Cellulose esters are valuable polymers which are useful in many plastic, film, coating and fiber applications. In coatings applications, cellulose esters are generally applied from organic solvent solutions.
U.S. Pat. No. 4,520,192 describes a process for preparing carboxyalkyl acetyl celluloses with a carboxyalkyl degree of substitution per anhydroglucose unit (DS) of 0.2-2.5 and an acetyl DS of 0.5-2.8 and the metal salts of these materials. The preparation of the carboxyalkyl acetyl cellulose is accomplished by converting carboxyalkyl cellulose, sodium salt, into its acid form by soaking in an aqueous acid solution of sulfuric acid, hydrochloric acid, nitric acid, or acetic acid. This is followed by washing with water, solvent exchange of the water with acetic acid, and reaction with acetic anhydride in the presence of a catalyst (sulfuric acid, perchloric acid, sulfoacetic acid or zinc chloride) to give a trisubstituted carboxy acetyl cellulose, i.e., carboxymethyl cellulose acetate, upon precipitation into water. They also claim a process for converting the carboxyalkyl acetyl cellulose product (acid form) to its corresponding sodium, potassium, calcium, or ammonium carboxylate salt. The acid form of the trisubstituted carboxyalkyl acetyl celluloses were insoluble in water and aqueous lower chain alcohol solutions. These materials were soluble in acetone and methylene chloride/ethanol 9/1. The sodium salt of the carboxyalkyl acetyl cellulose was soluble in water, an aqueous lower alkyl alcohol containing a large amount of water, or aqueous acetone; however, it was insoluble in methylene chloride/ethanol 9/1. We believe this process to yield a product containing an unneutralized strong acid with high sulfur levels. Consequently, this ester would be unstable under general drying conditions or other heat treatment. The process for converting the sodium salt form of carboxymethyl cellulose to the acid form is also described in Swiss Patent No. 247,440 by soaking in 10% sulfuric acid solution.
U.S. Pat. No. 3,435,027 describes a base catalyzed (sodium hydroxide) esterification of carboxymethyl cellulose (in the sodium salt form) in 70-85% acetone nonsolvent media with acetic, propionic, lactic, or stearyl anhydride. The procedure yields a product with a low degree of ester substitution and falls well short of a fully substituted cellulose. This reference claims a base catalyzed process for preparing cellulose ether-esters (containing from 0.1-18% acetyl, which corresponds to 0.01-0.97 DS (acetyl) from a water soluble cellulose ether in a nonsolvent media and products thereof.
USSR Patent 612933 describes a process for preparation of cellulose acetate ethers wherein an alkali activated cellulose (12% sodium hydroxide) is etherified with monochloroacetic acid followed by esterification with acetic anhydride in the presence of sulfuric acid catalyst. The process is limited to a low DS of the carboxymethyl substituent.
U.S. Pat. No. 3,789,117 discloses a process for preparing an enteric medicant coating from an organic solvent soluble cellulose derivative. The cellulose derivative's substitution has a carboxymethyl DS range of 0.3 to 1.2 in conjunction with at least one of the remaining hydroxyl groups being etherified or esterified. Ester groups, of which they do not indicate the degree of substitution, include acetyl, propionyl, butyryl, nitric, or higher fatty acids.
RO 96929 describes a carboxymethyl cellulose (CMC) acetate with a carboxymethyl degree of substitution of 0.5-3.0, acetyl DS of 0.4-2.9, and viscosity 150-1500 cP. This material was taught to be useful as an alkaline suspension stabilizer, solution thickener, and alkaline media binder. The material was prepared by mixing 70% acetic acid with CMC(Na salt), washing the acetic wet CMC with 50% acetic acid to remove the sodium acetate, and esterification of the acetic acid wet CMC-H with acetic anhydride for 1.5 hours at 50.degree.-110.degree. C. in the presence of sulfuric acid.
U.S. Pat. No. 5,008,385 reports cellulose derivatives that can be synthesized by homogeneous reaction in dimethylacetamide and/or N-methylpyrrolidine containing LiCl. Included in their examples was CMC acetate (carboxymethyl DS 0.13-0.23, acetyl DS 2.54-2.15). These materials were tested for use in the production of fibers, filaments, or membranes.
Carbohydrate Research, 13, pp.83-88, (1970) describes the preparation of CMC acetate by sulfuric acid catalyzed acetylation of CMC (carboxymethyl DS of 0.07) hydrolysis (acetylation and hydrolysis procedures taken from Malm, Ind. Eng. Chem., 38 (1946) 77), and evaluation of this material in membranes for reverse osmosis.
Holzforschung, 27(2), pp. 68-70, (1973) describes the rate of carboxymethylation and deacetylation of cellulose acetate in the presence of sodium hydroxide. This work showed that deacetylation and carboxymethylation occur simultaneously with the rate of deacetylation being faster than the rate of carboxymethylation. The highest carboxymethyl DS obtained was less than 0.1.
GB 2,284,421 discloses carboxymethyl cellulose alkanoates which are "lightly carboxymethylated", i.e., having a degree of substitution per anhydroglucose unit of less than 0.2. Such polymers are taught to be useful as a coating agent for paper and papermaking or as a bonding agent for non-woven fabric, or can be extruded to form filaments or film, or can be used to produce shaped articles or a sponge.